CN104294314B - A kind of coal ash for manufacturing is for the method for almag - Google Patents
A kind of coal ash for manufacturing is for the method for almag Download PDFInfo
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- CN104294314B CN104294314B CN201410484953.XA CN201410484953A CN104294314B CN 104294314 B CN104294314 B CN 104294314B CN 201410484953 A CN201410484953 A CN 201410484953A CN 104294314 B CN104294314 B CN 104294314B
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000010883 coal ash Substances 0.000 title claims abstract description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 106
- 230000004907 flux Effects 0.000 claims abstract description 43
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 31
- 239000010881 fly ash Substances 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 25
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000011780 sodium chloride Substances 0.000 claims abstract description 16
- 239000001103 potassium chloride Substances 0.000 claims abstract description 15
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 11
- 230000008023 solidification Effects 0.000 claims abstract description 11
- 238000007711 solidification Methods 0.000 claims abstract description 11
- 230000008021 deposition Effects 0.000 claims abstract description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 229910052782 aluminium Inorganic materials 0.000 claims description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 29
- 239000004411 aluminium Substances 0.000 claims description 28
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 16
- 238000005660 chlorination reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002386 leaching Methods 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract description 2
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 26
- 235000002639 sodium chloride Nutrition 0.000 description 14
- 235000011164 potassium chloride Nutrition 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000009866 aluminium metallurgy Methods 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910000632 Alusil Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to nonferrous metallurgy field, relate to a kind of coal ash for manufacturing method for almag.The technical scheme is that and produce aluminium chloride initially with flyash acidleach, the electrolyte system then used is made up of flux, molten matter and additive, and wherein the composition of flux according to mass percent is: NaCl:0 60%, KCl:25 75%, MgCl2: 0 66%, it is subsequently adding molten matter AlCl accounting for flux quality 5 50%3, account for the LiCl Additive of flux quality 0 5%, 0 5% additive KF, 0 5% additive MgF2Or 0 5% additive A lF3, wherein melt matter AlCl3Adding from bottom of electrolytic tank, controlling voltage across poles is 2.3 3.3V, cathode-current density 0.5 1.5A/cm2, electrolysis temperature is 450 ~ 500 DEG C, and electrolytic process Anodic side produces chlorine, recovered re-uses, at negative electrode side deposition solidification state almag.The inventive method power consumptive province, electrolysis temperature is low, and production cost is low, solves aluminium chloride evaporation problems and electrolysis produces dendrite problems, and non-environmental-pollution, equipment easily realizes.
Description
Technical field
The invention belongs to nonferrous metallurgy field, relate to a kind of coal ash for manufacturing method for almag.
Background technology
Traditional metallic aluminium production method is Hall-Ai Lute (Hall-Heroult) method, 1886, the method that American Hall and Frenchman Herout has invented cryolite-alumina aluminum production by fused-salt electrolysis simultaneously, i.e. do electrode material with carbon materials, solvent is made with ice crystal, aluminum oxide does solute, carries out the method that molten-salt electrolysis produces aluminium at a temperature of 950-1000 DEG C.Aluminum oxide source up to the present mainly with alkali leach method obtains, i.e. with alkali (industrial caustic soda NaOH or soda ash Na2CO3) process bauxite, make the aluminum oxide in ore become solvable sodium aluminate.After carrying out the sodium aluminate solution of purification decomposing precipitation aluminium hydroxide, separating, washing and calcining, obtain product aluminum oxide.
Along with the strategic requirement of the energy, environmental protection pressure and sustainable development, people are carrying out the technical research of new method aluminium metallurgy always.
Aluminium metallurgy new method mainly includes two big classes at present: one is to produce alusil alloy with direct charcoal reduction aluminium ore under electric arc furnaces high temperature；Two is that aluminium chloride electrolysis produces fine aluminium.
German Bunsen in 1854 and France Deville electrolyzing fused AlCl respectively3NaCl obtains metallic aluminium, and Alcoa (Alcoa) declaration in 1973 is succeeded in developing aluminium chloride molten salt electrolysis and produced aluminium (US3893899, US3785941, US3725222).The method of Alcoa company be electrolytic cell be multicavity tray, electrode is the bipolar electrode configured up and down, and die opening is approximately 1.3cm, and electrolyte consists of (weight/mass percentage composition): AlCl3=5%, NaCl=53%, LiCl=40%, electrolyte is also containing a small amount of MgCl2、KCl、CaCl2.Electrolytic cell daily output aluminium 13t, power consumption is every kg aluminium 9.5kW h, and current efficiency is 87%.Patent CA502977, CN93107810.5, US3518172, US3725222, US3103472, US2919234, US4919771 disclose similar content, these methods are to use with NaCl as primary solvent mostly, with aluminium chloride as solute, temperature controls in the molten-salt electrolysis carried out above of aluminium fusing point.Its subject matter existed is that aluminium chloride adds electrolyte with gaseous state, and with the presence of aluminium chloride evaporant in chlorine gas phase, temperature is high, and heat loss is big.Patent US1854684 discloses electrolyte ingredient AlCl3The method of 82%, NaCl 18%, its current density 4.2A/ square, 3.2V, 160 DEG C.Japan Patent (" Application Publication " clear 56-15714,1981) discloses electrolyte ingredient (mass percent): AlCl3
76.3%, KCl 9.3%, NaCl 14.5%, thermostat keeps 134-150 DEG C, anodic current density 0.43A/cm2, pole span 10mm,
The method of voltage 8.2-9.5V.It is low that the two method is mainly characterized by electrolysis temperature, and aluminium chloride vapour is easily controlled, but metal is crystal grain state, collects difficulty, it addition, easily generate the greatest drawback that dendrite is the existence of the method.
The research aluminium chloride source of aluminium chloride electrolysis in early days is obtained by aluminum oxide chlorination mostly, and production cost is higher, adds some difficulties in engineering, never obtains industrial applications.
Summary of the invention
The problem existed for prior art, the present invention provides a kind of coal ash for manufacturing for the method for almag, purpose is to obtain aluminium chloride by sulfuric acid to leach flyash, uses low melting point, high conductivity electrolyte electrolytic chlorination aluminium to produce almag, it is achieved low temperature and low cost prepare almag.
The technical scheme realizing the object of the invention follows the steps below:
(1) aluminium chloride is produced in flyash acidleach: filtered levigate for flyash mixing with sulfuric acid afterwards after leaching is reacted, add water in filter residue, heating is boiled molten, dissolution reactant, is filtered to remove residue, obtains aluminum sulfate solution, concentrate by aluminum sulfate solution evaporative crystallization or by aluminum sulfate solution, with mixed in hydrochloric acid, then pass to HCl gas, separate out AlCl3·6H2O crystal, drying dehydration prepares anhydrous AlCl3；
(2) electrolytic chlorination aluminium produces almag: using graphite or carborundum as bipolar electrode, pole span is 1-3cm, and the electrolyte system of employing is made up of flux, molten matter and additive, and wherein the composition of flux according to mass percent is: NaCl: 0-60%, KCl:25-75%, MgCl2: 28.5-66%, it is subsequently adding molten matter AlCl accounting for flux quality 5-50%3, account for the LiCl Additive of flux quality 0-5%, 0-5% additive KF, 0-5% additive MgF2Or 0-5% additive A lF3, wherein melt matter AlCl3Adding from bottom of electrolytic tank, control voltage across poles is 2.3-3.3V, cathode-current density 0.5-1.5A/cm2, electrolysis temperature is 450 ~ 500 DEG C, and electrolytic process Anodic side produces chlorine, recovered re-uses, at negative electrode side deposition solidification state almag.
Flyash is milled to 100-200 μm by described step (1), with sulfuric acid according to 1:(4.5～10) mass ratio mix, at 280～350 DEG C, react 2.5 ~ 3h, described sulfuric acid be mass concentration be 75～the sulfuric acid of 98% or leach filter after the sulfuric acid that returns of the sulfuric acid that returns or the displacement of hydrochloric acid and aluminum sulfate.
The described filter residue in step (1) adds the water of 3～5 times of quality, at 65～80 DEG C, boils molten 45～60 minutes.It is 1.4g/mL that the described aluminum sulfate solution in step (1) is concentrated into density.
The mass concentration of the described hydrochloric acid in step (1) is 15～38%.
The described AlCl in step (1)3·6H2O crystal drying and dehydrating at 110-150 DEG C prepares anhydrous AlCl3Crystal.
Compared with prior art, the feature of the present invention and providing the benefit that:
The inventive method is using discarded flyash as raw material, obtains almag, has the advantage of energy-saving and environment friendly.
Technical solution of the present invention is using sodium chloride, potassium chloride, magnesium dichloride-based chloride system as electrolyte, significantly reduce molten-salt electrolysis and prepare the temperature of metallic aluminium, prior art generally use cryolite-alumina molten-salt electrolysis obtain metallic aluminium, generally at 900 ~ 1000 DEG C, and in the present invention, by controlling sodium chloride, potassium chloride and the component ratio of magnesium chloride, make the liquidus temperature of electrolyte less than 500 DEG C, addition along with solute aluminium chloride, liquidus temperature reduces further, forms a kind of preferably aluminium chloride electrolyte system.Therefore, by controlling electrolyte system composition in the present invention, electrolysis temperature is controlled at 450 ~ 500 DEG C.
The almag obtained in the present invention is at electrode surface with solid deposited, does not produce dendrite, easily collects.
To sum up, the inventive method power consumptive province, electrolysis temperature is low, and production cost is low, solves aluminium chloride evaporation problems and electrolysis produces dendrite problems, and non-environmental-pollution, equipment easily realizes.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
The flyash composition used in the embodiment of the present invention is as shown in table 1.
Table 1 flyash main component (weight/mass percentage composition %)
| Al2O3 | SiO2 | Fe2O3 | CaO | TiO2 | MgO | MnO | Other |
| 41.20 | 48.49 | 3.37 | 3.31 | 1.30 | 0.20 | 0.013 | 2.117 |
Embodiment 1
(1) aluminium chloride is produced in flyash acidleach: flyash is milled to 100-200 μm, filter after mixing leaching reaction with sulfuric acid according to the mass ratio of 1:4.5, at 280 DEG C, react 3h, in filter residue, add the water of 3 times of quality, molten 60 minutes are boiled at 65 DEG C, dissolution reactant, is filtered to remove residue, obtains aluminum sulfate solution, by aluminum sulfate solution evaporative crystallization, it is the mixed in hydrochloric acid of 38% with mass concentration, then passes to HCl gas, separate out AlCl3·6H2O crystal, at 110 DEG C, drying and dehydrating prepares anhydrous AlCl3；
(2) electrolytic chlorination aluminium produces almag: using graphite as bipolar electrode, pole span is 1cm, and the electrolyte system of employing is made up of flux, molten matter and additive, and wherein the composition of flux according to mass percent is: NaCl: 23.7 %, KCl:33.5%, MgCl2: 42.8%, it is subsequently adding molten matter AlCl accounting for flux quality 5%3, account for the LiCl Additive of flux quality 5%, wherein AlCl3Adding from bottom of electrolytic tank, control voltage across poles is 2.3V, cathode-current density 0.85/cm2, electrolysis temperature is 450 DEG C, and electrolytic process Anodic side produces chlorine, recovered re-uses, and at the negative electrode side attachment almag in solidification state, in chemical analysis, alloy, the content of Al and Mg is respectively 94.7% and 5.3%.
Embodiment 2
(1) aluminium chloride is produced in flyash acidleach: flyash is milled to 100-200 μm, filter after mixing leaching reaction with sulfuric acid according to the mass ratio of 1:10, at 300 DEG C, react 2.8h, in filter residue, add the water of 4 times of quality, molten 50 minutes are boiled at 75 DEG C, dissolution reactant, is filtered to remove residue, obtains aluminum sulfate solution, it is 1.4g/mL that aluminum sulfate solution is concentrated into density, it is the mixed in hydrochloric acid of 25% with mass concentration, then passes to HCl gas, separate out AlCl3·6H2O crystal, at 120 DEG C, drying and dehydrating prepares anhydrous AlCl3；
(2) electrolytic chlorination aluminium produces almag: using carborundum as bipolar electrode, pole span is 1.5cm, and the electrolyte system of employing is made up of flux, molten matter and additive, and wherein flux according to mass percent is: NaCl: 39.6%, KCl:26.5%, MgCl2: 33.9%, it is subsequently adding molten matter AlCl accounting for flux quality 10%3, account for the additive KF of flux quality 5%, wherein AlCl3Adding from bottom of electrolytic tank, control voltage across poles is 2.8V, cathode-current density 1.13A/cm2, electrolysis temperature is 430 DEG C, and electrolytic process Anodic side produces chlorine, recovered re-uses, and at the negative electrode side attachment almag in solidification state, in alloy, the content of Al and Mg is respectively 85.3% and 14.7%.
Embodiment 3
(1) aluminium chloride is produced in flyash acidleach: flyash is milled to 100-200 μm, filter after mixing leaching reaction with sulfuric acid according to the mass ratio of 1:6, at 350 DEG C, react 2.5h, in filter residue, add the water of 5 times of quality, molten 45 minutes are boiled at 80 DEG C, dissolution reactant, is filtered to remove residue, obtains aluminum sulfate solution, it is 1.4g/mL that aluminum sulfate solution is concentrated into density, it is the mixed in hydrochloric acid of 18% with mass concentration, then passes to HCl gas, separate out AlCl3·6H2O crystal, at 130 DEG C, drying and dehydrating prepares anhydrous AlCl3；
(2) electrolytic chlorination aluminium produces almag: using graphite as bipolar electrode, pole span is 2.5cm, and the electrolyte system of employing is made up of flux, molten matter and additive, and wherein the composition of flux according to mass percent is: KCl:67.0%, MgCl2: 33.0%, it is subsequently adding molten matter AlCl accounting for flux quality 20%3, account for the LiCl Additive of flux quality 4%, wherein AlCl3Adding from bottom of electrolytic tank, control voltage across poles is 2.7V, cathode-current density 0.97A/cm2, electrolysis temperature is 500 DEG C, and electrolytic process Anodic side produces chlorine, recovered re-uses, and at the negative electrode side attachment almag in solidification state, in alloy, the content of Al and Mg is respectively 89.5% and 10.5%.
Embodiment 4
(1) aluminium chloride is produced in flyash acidleach: flyash is milled to 100-200 μm, filter after mixing leaching reaction with sulfuric acid according to the mass ratio of 1:8, at 320 DEG C, react 2.8h, in filter residue, add the water of 3.5 times of quality, molten 50 minutes are boiled at 75 DEG C, dissolution reactant, is filtered to remove residue, obtains aluminum sulfate solution, it is 1.4g/mL that aluminum sulfate solution is concentrated into density, it is the mixed in hydrochloric acid of 28% with mass concentration, then passes to HCl gas, separate out AlCl3·6H2O crystal, at 140 DEG C, drying and dehydrating prepares anhydrous AlCl3；
(2) electrolytic chlorination aluminium produces almag: using carborundum as bipolar electrode, pole span is 2cm, and the electrolyte system of employing is made up of flux, molten matter and additive, and wherein flux composition according to mass percent is: KCl:34%, MgCl2: 66%, it is subsequently adding molten matter AlCl accounting for flux quality 30%3, account for the AlF of flux quality 3%3, wherein AlCl3Adding from bottom of electrolytic tank, control voltage across poles is 3.3V, cathode-current density 0.49A/cm2, electrolysis temperature is 500 DEG C, and electrolytic process Anodic side produces chlorine, recovered re-uses, and at the negative electrode side attachment almag in solidification state, in alloy, the content of Al and Mg is respectively 68.5% and 31.5%.
Embodiment 5
(1) aluminium chloride is produced in flyash acidleach: flyash is milled to 100-200 μm, filter after mixing leaching reaction with sulfuric acid according to the mass ratio of 1:5, at 300 DEG C, react 2.8h, in filter residue, add the water of 4.5 times of quality, molten 50 minutes are boiled at 70 DEG C, dissolution reactant, is filtered to remove residue, obtains aluminum sulfate solution, by aluminum sulfate solution evaporative crystallization, it is the mixed in hydrochloric acid of 38% with mass concentration, then passes to HCl gas, separate out AlCl3·6H2O crystal, at 150 DEG C, drying and dehydrating prepares anhydrous AlCl3；
(2) electrolytic chlorination aluminium produces almag: using graphite as bipolar electrode, pole span is 2cm, and the electrolyte system of employing is made up of flux and molten matter, and wherein flux composition according to mass percent is: NaCl: 22.7%, KCl:48.8%, MgCl2: 28.5%, it is subsequently adding molten matter AlCl accounting for flux quality 50%3, wherein AlCl3Adding from bottom of electrolytic tank, control voltage across poles is 3.0V, cathode-current density 0.98A/cm2, electrolysis temperature is 400 DEG C, and electrolytic process Anodic side produces chlorine, recovered re-uses, and at the negative electrode side attachment almag in solidification state, in alloy, the content of Al and Mg is respectively 78.9% and 21.1%.
Embodiment 6
(1) aluminium chloride is produced in flyash acidleach: flyash is milled to 100-200 μm, filter after mixing leaching reaction with sulfuric acid according to the mass ratio of 1:9, at 280 DEG C, react 3h, in filter residue, add the water of 5 times of quality, molten 60 minutes are boiled at 65 DEG C, dissolution reactant, is filtered to remove residue, obtains aluminum sulfate solution, it is 1.4g/mL that aluminum sulfate solution is concentrated into density, it is the mixed in hydrochloric acid of 15% with mass concentration, then passes to HCl gas, separate out AlCl3·6H2O crystal, at 150 DEG C, drying and dehydrating prepares anhydrous AlCl3；
(2) electrolytic chlorination aluminium produces almag: using carborundum as bipolar electrode, pole span is 3cm, and the electrolyte system of employing is made up of flux, molten matter and additive, and wherein flux composition according to mass percent is: NaCl: 21.3%, KCl:24.8%, MgCl2: 53.9%, it is subsequently adding molten matter AlCl accounting for flux quality 40%3, account for the LiCl of flux quality 1%, wherein AlCl3Adding from bottom of electrolytic tank, control voltage across poles is 3.2V, cathode-current density 0.67A/cm2, electrolysis temperature is 400 DEG C, and electrolytic process Anodic side produces chlorine, recovered re-uses, and at the negative electrode side attachment almag in solidification state, in alloy, the content of Al and Mg is respectively 66.6% and 33.4%.
Embodiment 7
(1) aluminium chloride is produced in flyash acidleach: flyash is milled to 100-200 μm, filter after mixing leaching reaction with sulfuric acid according to the mass ratio of 1:10, at 300 DEG C, react 3h, in filter residue, add the water of 5 times of quality, molten 60 minutes are boiled at 65 DEG C, dissolution reactant, is filtered to remove residue, obtains aluminum sulfate solution, by aluminum sulfate solution evaporative crystallization, it is the mixed in hydrochloric acid of 20% with mass concentration, then passes to HCl gas, separate out AlCl3·6H2O crystal, at 120 DEG C, drying and dehydrating prepares anhydrous AlCl3；
(2) electrolytic chlorination aluminium produces metallic aluminium: using carborundum as bipolar electrode, pole span is 2.8cm, the electrolyte system used is made up of flux, molten matter and additive, wherein the composition of additive according to mass percent is: NaCl: 25%, KCl:75%, is subsequently adding molten matter AlCl accounting for flux quality 45%3, account for the KF of flux quality 2%, wherein AlCl3Adding from bottom of electrolytic tank, control voltage across poles is 2.9V, cathode-current density 1.4A/cm2, electrolysis temperature is 500 DEG C, and electrolytic process Anodic side produces chlorine, recovered re-uses, and at the negative electrode side attachment metallic aluminium in solidification state, through chemical analysis, the quality purity obtaining metallic aluminium is 99.5%.
Embodiment 8
(1) aluminium chloride is produced in flyash acidleach: flyash is milled to 100-200 μm, filter after mixing leaching reaction with sulfuric acid according to the mass ratio of 1:9, at 350 DEG C, react 2.5h, in filter residue, add the water of 5 times of quality, molten 45 minutes are boiled at 80 DEG C, dissolution reactant, is filtered to remove residue, obtains aluminum sulfate solution, by aluminum sulfate solution evaporative crystallization, it is the mixed in hydrochloric acid of 15% with mass concentration, then passes to HCl gas, separate out AlCl3·6H2O crystal, at 110 DEG C, drying and dehydrating prepares anhydrous AlCl3；
(2) electrolytic chlorination aluminium produces metallic aluminium: using carborundum as bipolar electrode, pole span is 3cm, and the electrolyte system of employing is made up of flux, molten matter and additive, and wherein flux composition is by mass percentage: NaCl: 60%, KCl:40%, is subsequently adding the AlCl accounting for flux quality 50%3, account for the AlF of flux quality 5%3, wherein AlCl3Adding from bottom of electrolytic tank, control voltage across poles is 3.1V, cathode-current density 1.5A/cm2, electrolysis temperature is 500 DEG C, and electrolytic process Anodic side produces chlorine, recovered re-uses, and at the negative electrode side attachment metallic aluminium in solidification state, through chemical analysis, the quality purity obtaining metallic aluminium is 99.6%.
Claims (6)
1., with coal ash for manufacturing for a method for almag, follow the steps below:
(1) aluminium chloride is produced in flyash acidleach: filtered levigate for flyash mixing with sulfuric acid afterwards after leaching is reacted, add water in filter residue, heating is boiled molten, dissolution reactant, is filtered to remove residue, obtains aluminum sulfate solution, concentrate by aluminum sulfate solution evaporative crystallization or by aluminum sulfate solution, with mixed in hydrochloric acid, then pass to HCl gas, separate out AlCl3·6H2O crystal, drying dehydration prepares anhydrous AlCl3；
It is characterized in that:
(2) electrolytic chlorination aluminium produces almag: using graphite or carborundum as bipolar electrode, pole span is 1-3cm, the electrolyte system used is by flux, molten matter and additive forms or is made up of flux and molten matter, wherein the composition of flux according to mass percent is: NaCl: 0-60%, KCl:25-75%, MgCl2: 28.5-66%, it is subsequently adding molten matter AlCl accounting for flux quality 5-50%3, account for the LiCl Additive of flux quality 0-5%, 0-5% additive KF, 0-5% additive MgF2Or 0-5% additive A lF3, wherein melt matter AlCl3Adding from bottom of electrolytic tank, control voltage across poles is 2.3-3.3V, cathode-current density 0.5-1.5A/cm2, electrolysis temperature is 450 ~ 500 DEG C, and electrolytic process Anodic side produces chlorine, recovered re-uses, at negative electrode side deposition solidification state almag.
A kind of coal ash for manufacturing the most according to claim 1 is for the method for almag, it is characterized in that flyash is milled to by described step (1) 100-200 μm, with sulfuric acid according to 1:(4.5～10) mass ratio mix, at 280～350 DEG C, react 2.5 ~ 3h, described sulfuric acid be mass concentration be 75～98% sulfuric acid leaching filter after the sulfuric acid that returns of the sulfuric acid that returns or the displacement of hydrochloric acid and aluminum sulfate.
A kind of coal ash for manufacturing the most according to claim 1 is for the method for almag, it is characterised in that adds the water of 3～5 times of quality in the described filter residue in step (1), boils molten 45～60 minutes at 65～80 DEG C.
A kind of coal ash for manufacturing the most according to claim 1 is for the method for almag, it is characterised in that it is 1.4g/mL that the described aluminum sulfate solution in step (1) is concentrated into density.
A kind of coal ash for manufacturing the most according to claim 1 is for the method for almag, it is characterised in that the mass concentration of the described hydrochloric acid in step (1) is 15～38%.
A kind of coal ash for manufacturing the most according to claim 1 is for the method for almag, it is characterised in that the described AlCl in step (1)3·6H2O crystal drying and dehydrating at 110-150 DEG C prepares anhydrous AlCl3Crystal.
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| US4110178A (en) * | 1977-05-17 | 1978-08-29 | Aluminum Company Of America | Flow control baffles for molten salt electrolysis |
| EP0611837A1 (en) * | 1992-08-04 | 1994-08-24 | MARAKUSHEV, Alexei Alexandrovich | Method for obtaining aluminium from alumina-containing raw material |
| CN102502665A (en) * | 2011-11-22 | 2012-06-20 | 中国铝业股份有限公司 | Method for comprehensively recovering valuable elements in coal ash |
| CN102849767A (en) * | 2012-04-10 | 2013-01-02 | 沈阳金博新技术产业有限公司 | Method for preparing alumina by using power plant fly ash |
| CN102912382A (en) * | 2012-10-26 | 2013-02-06 | 哈尔滨工程大学 | Electrolytic method for manufacturing aluminum-manganese alloy in fluoride-chloride molten salt system |
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|---|---|---|---|---|
| US4110178A (en) * | 1977-05-17 | 1978-08-29 | Aluminum Company Of America | Flow control baffles for molten salt electrolysis |
| EP0611837A1 (en) * | 1992-08-04 | 1994-08-24 | MARAKUSHEV, Alexei Alexandrovich | Method for obtaining aluminium from alumina-containing raw material |
| CN102502665A (en) * | 2011-11-22 | 2012-06-20 | 中国铝业股份有限公司 | Method for comprehensively recovering valuable elements in coal ash |
| CN102849767A (en) * | 2012-04-10 | 2013-01-02 | 沈阳金博新技术产业有限公司 | Method for preparing alumina by using power plant fly ash |
| CN102912382A (en) * | 2012-10-26 | 2013-02-06 | 哈尔滨工程大学 | Electrolytic method for manufacturing aluminum-manganese alloy in fluoride-chloride molten salt system |
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Effective date of registration: 20180319 Address after: 110044, building 2, building 20, Beihai street, Dadong District, Liaoning, Shenyang, 251, Beihai Patentee after: Li Jingjiang Address before: 110014, No. 21-1, Temple Road, thirteen weft Road, Shenhe District, Liaoning, Shandong, Shenyang Patentee before: Shenyang Jinbo New technology Industry Co., Ltd. |